US2668162A - Preparation of high molecular weight polyhydroxyacetic ester - Google Patents

Preparation of high molecular weight polyhydroxyacetic ester Download PDF

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US2668162A
US2668162A US277726A US27772652A US2668162A US 2668162 A US2668162 A US 2668162A US 277726 A US277726 A US 277726A US 27772652 A US27772652 A US 27772652A US 2668162 A US2668162 A US 2668162A
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glycolide
antimony
polymer
polyhydroxyacetic
molecular weight
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Charles E Lowe
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D319/00Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/101,4-Dioxanes; Hydrogenated 1,4-dioxanes
    • C07D319/121,4-Dioxanes; Hydrogenated 1,4-dioxanes not condensed with other rings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08Lactones or lactides

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  • This invention relates to the preparation of polymeric plastic materials and :more particularly to an improved processior -preparing high molecular weight polyhydroxyacetic ester.
  • An object of the present invention is to produce by a simple and economical process, high molecular weight polyh-ydroxyacetic esters :capable of .being'm'elteextruded into strong'or-ientable fibers..tand. self supporting thinwfilm.
  • An other object is to produce such .polyhydroxy acetic esters directly from glycolide.
  • hydroxyacetic acid has been polymerized under tain conditions hereinalfter specified, 'be,.poly-.
  • the present process comprises heating pure, dryglycOlideiin, an inertatmosphere, i. e., in an atmosphere of nitrogen, in the presence of a catalytic ,quantity of. an antimony compound from thelgroupconsisting of. antimony trioxidean'd antimony'trihali'des at a temperature between 150 C. andi'24'5 'Pref 1- erabl y, the reactionjispermittedto-proceed at a.
  • antimony trifiuoride is the vprefen ed catalyst
  • any antimony-.compnun'dxfrom the:group consisting of antimony .trioxi'dez and antimony trihalides, such .as antimony :tri'chl'oritle, anti mony .tribromiderand antimony tri-ti'oiiili'e :e'fieetively catalyzes the reaction.
  • Catalyst-concentrations ranging .from 0:01???) ttoil';li%- 'mayr be employed, andv 0.03%, iba'sedfsupon the weight of glycolide or combined weiglitstof glycolide land lactide 101 other lacti'cles, ii's preferred.
  • the'catalyst concentration-is decreasedibelow- 0.01% or increased -:a;bove.;0sls%' them'elt: viscosity of the 'resulting- -polym-eriis l'ower than that which may be obtained-ioperating withinithe specified range of catalyst concentration.
  • the process of the present invention zmay be employed with advantage toprepare copolymers of glycolide withsmall quantities-e. g-., up' 'to 15%, of other lactidos such as "lactide and 'disalicylide.
  • acopolymerof /10 -glycolideilactide offers two advantagesoverthe 'homopolymer-'of "g'lycolide;
  • One advantage is thatthe melting"point-ofthe copolymer is lower than "the homopolymerf-b eing in the neighborhood of 200 6.
  • glycolide The presence of water or acid impurities in glycolide tends to retard polymerization, and the resulting polyhydroxyacetic ester will not have a molecular weight suitable for extrusion into films or filaments.
  • polymerization of impure glycolide usually results in the formation of a polymer having a melt viscosity less than 400 poises, while pure glycolide gives polymers having melt viscosities up to 50,000 poises.
  • polyhydroxyacetic esters having melt viscosities substantially greater than 27,000 poises are extremely difiicult to extrude into films or filaments.
  • Pure, dry (i. e., anhydrous) glycolide may conveniently be prepared in high yield by the depolymerization of low molecular weight polyhydroxyacetic ester which is formed as a by-product in various known processes of converting hydroxyacetic acid directly to high molecular weight polyhydroxyacetic ester.
  • the following example typifies the preparation of glycolide by this method:
  • Example A A charge of 4,000 parts of crude hydroxyacetic acid flake was heated at atmospheric pressure until the temperature of the liquid reached 175- 185 C. The temperature was maintained at this range for 2 hours or silghtly longer until water ceased to distill. The pressure was then reduced over a period of /2 hour to 150 mm. of mercury; and the temperature was maintained between 175-185 C. for 2 hours, or, again for a slightly longer time, until water ceased to distill. The product obtained was poured into an enamel pan and, after solidification, the white, brittle polymer was reduced to a free-flowing powder in a cutting machine.
  • the apparatus for depolymerizing the above polyhydroxyacetic ester to form glycolide consisted of a three-necked reaction vessel equipped with a stainless steel stirrer, and provision for introducing the powdered polymer in increments through one neck and for take-on of the glycolide distillate through a downward connection tube wound with an electrical strip heater.
  • a supply vessel containing the powdered polymer was attached by means of heavy-walled, flexible tubing to a stopcock so that the portion above the stopcock could be alternately filled and discharged into the reaction vessel.
  • a steady stream of nitrogen was introduced through the polymer inlet tube to prevent accumulation or" glycolide distillate and consequent plugging.
  • a receiver was cooled in an ice water bath and equipped with an air condenser to trap most of the uncondensed glycolide. Since the nitrogen stream tended to carry glycolide beyond the receiver, three traps Were interposed to protect the pump. One trap was a three-necked vessel filled with steel wool and immersed in an ice water bath, and the other two were standard Dry Ice-acetone tra s.
  • the glycolide was purified by 2 or 3 recrystallizations from chemically pure ethyl acetate. In all cases, the crude glycolide was added to approximately twice its weight of ethyl acetate; solution was efiected at the boiling point; decolorizing charcoal was added; and reflux continued for hour. The solution was filtered while hot; cooled; and white glycolide crystals were obtained on filtering and drying. Further recrystallizations were conducted in a similar manner, but the decolorizing charcoal treatment was omitted.
  • Example 1 Antimony trifiuoride (0.03% by weight of dry glycolide) was added to 2,300 parts of pure, dry glycolide in a closed reaction vessel. Nitrogen was allowed to pass over the surface of the material in the vessel. The reaction vessel was heated to C. by means of an oil bath and the contents stirred for one hour at that temperature. Stirring was stopped at this point since the material had become too viscous; and heating at 195 C. was maintained for one more hour, after which the temperature was quickly raised to 230 C. and maintained for hour. After solidification, the resulting polymer (M. P. 215-220 C.) was pulverized and further dried. The resulting polyhydroxyacetic ester had a melt viscosity of 20,000 poises at 245 C. and 6,900 poises at 255 C. The ground polymer was extruded into a tough, colddrawable, stretchable, and self-supporting film. The film had a melt viscosity of 1,800 poises at 245 C.
  • the most characteristic single indication of plastic properties in high molecular weight polyhydroxyacetic esters is the ability of the polymer to form a highly viscous melt. Since the polymers degrade with increasing rapidity as the temperature is raised above the melting point, a standard temperature of 245 C. was selected for comparative tests. This is near the melting point but is sufficiently above it to avoid melting difiiculties. It has been found that at 245 C. a polyhydroxyacetic ester must have a melt viscosity, measured by the method of Flory (Journal of the American Chemical Society, 62, 1057 (1940) of at least 400 poises before it can be molded into useful shaped articles, the preferred viscosity range being from 1,000 to 10,000 poises for extrusion into fibers and films.
  • the polymer melt is too fluid and non-adherent to handle properly during forming operations; and the shaped products are increasingly brittle, non-cohesive and weak.
  • the melt viscosity can be so high that the polymer is difficult to mold or extrude.
  • Example 2 Antimony trichloride (approximately 0.10% by 1
  • Example 3 Antimony trioxide (0.03% by weight of dry glycolide) was added to 20.0 parts of pure, dry glycolide in a tubular reaction vessel (diameter 0.5") provided with a side-arm near the top of the tube. Nitrogen was allowed to pass over the surface of the material in the tube end out through the side-arm. The tube was heated to 155 C. by means of a vapor bath and maintained at that temperature for 2 hours. Then the temperature was raised to 241 C. in an appropriate vapor bath. After 1.8 hours at 241 C., a polymer was produced having a melt viscosity of 4,300 poises at 241 0.
  • Example 4 Antimony trifiuoride (0.03% based upon the combined weight of glycolide and lactide) was added to 4.5 parts of pure, dry glycolide and 0.5 part of pure, dry lactide in a reaction vessel. Nitrogen was allowed to pass over the surface of the material in the vessel. The reaction vessel was heated to 195-200 C. by means of an oil bath and maintained at that temperature for 2% hours. Stirring of the reaction mixture was stopped after one hour because the material became too viscous. The resulting polymer was allowed to cool, and the solidified material was pulverized to a powder. After further drying, the
  • polymer (M. P. ZOO-205 C.) had a meltviscosity of 15,000 poises at 218 C. and a melt viscosity of 7,000 poises at 245 C.
  • the polymer was extruded into a tough, clear, cold-drawable, stretchable and self-supporting film at 210 C.
  • the resulting film had a melt viscosity of 1,300 poises at 218 C.
  • a particular advantage of the present invention is that it provides a process of forming high molecular weight polyhydroxyacetic esters by polymerizing a by-product of known processes for preparing the polymeric ester, glycolide.
  • a process for preparing polyhydroxyacetic esters which comprises polymerizing glycolide by heating glycolide, free of Water and acid impurities, at a temperature of from about C. to about 245 C. in the presence of a catalytic amount of an antimony compound from the group consisting of antimony trioxide and antimony trihalides.
  • a process for preparing polyhydroxyacetic esters which comprises heating glycolide, free of water and acid impurities, at a temperature of from about 150 C. to about 245 C. in the presence of from 0.01% to 1.0% by weight, based on the weight of glycolide, of an antimony compound from the group consisting of antimony trioxide and antimony trihalides.
  • a process for preparing polyhydroxyacetic ester homopolymer which comprises polymerizing lycolide by initially heating glycolide, free of water and acid impurities, in an atmosphere of inert gas, at a temperature of from 150 C. to 200 0., to form a low molecular weight polymer, and thereafter heating the polymer at a temperature of from 220 C. to 245 C. until a polymer having a melt viscosity at 245 C. of at least 400 poises is obtained, the entire reaction being carried outin the presence of from 0.01% to 1.0% by weight, based on the weight of glycolide, of an antimony compound from the group consisting of antimony trioxide and antimony trihalides as catalyst.

Description

Iatented Feb. 2, 1954 UNITED was PATENT oil-"rice:
- 'B P RA :QN:"Q GH. MOLECULAR IGgHT. LESTER .BOLYHYDROXYACETIC.
TNo rawi g, Application Marshal), 1,952,,
This invention relates to the preparation of polymeric plastic materials and :more particularly to an improved processior -preparing high molecular weight polyhydroxyacetic ester.
An object of the present invention is to produce by a simple and economical process, high molecular weight polyh-ydroxyacetic esters :capable of .being'm'elteextruded into strong'or-ientable fibers..tand. self supporting thinwfilm. An other object is to produce such .polyhydroxy acetic esters directly from glycolide. These and other objects will more clearly appear hereinafter.
In processes heretofore employed for the prep,- aration of high molecular weight polyhydroxyacetic esters of the general formula:
hydroxyacetic acid has been polymerized under tain conditions hereinalfter specified, 'be,.poly-.
merized to, produce fiber- .andfilm-Jforming polyhydroxyaceticiesters such as .are ,producediby thebefore-mentioned polymerization of 'hydrox-yacetic acid.
The present invention, 'therefOreQbrieflystated,
ompris s h at n p r lycolide in the presence of a catalytic amount of an antimonycompound from the group consisting of antimbnytrioxi'de and antimony 'trihalides.
"More specifically, the present process comprises heating pure, dryglycOlideiin, an inertatmosphere, i. e., in an atmosphere of nitrogen, in the presence of a catalytic ,quantity of. an antimony compound from thelgroupconsisting of. antimony trioxidean'd antimony'trihali'des at a temperature between 150 C. andi'24'5 'Pref 1- erabl y, the reactionjispermittedto-proceed at a.
temperaturebelow the meltingflpoint of thepolyhydroxyacetic' ester in order to,initiate,polymer-. ization, while minimizing darkening of the molten mass, foraperiod just s'horto fthejtime atwhich solidification "of the polymer produced com memos and thereafter the temperature is raised above the melting point to prevent solidification of the'po'lymer to "complete polymer zat on, n to permitmelt extrusion. Usuallminthepreparationof the polyhydroxyacetic-ester -from glycolide, the initial portion of the reaction is carried out at a tempQra-tureefirom 150 C.-200 C. and thereafter the temperature is raised to 220 -C.-.245
The melting point. ofthe-:polyhydroxyacetic; ester is-in the, nBighbIOIhOQdi'iOf; 21:5. 220f 16; Consequently, .in the preferred procedure, the initial portion of theireaction;iszcaazriedsoutz-ata, temperaturenf from-150910;. :to 290 3 "anrlarthe latter portion :of the .reaotionzissca-rried with-1: in the range 220=G-. -.-.2452. ,lfsuailwappreeiable degradation of the polymeritakes.:placeabove 245 C.; and itis preierredtto carry outthed'at-r terportion of the :reaction-ratiartemperaturesonlyslightly, i. e., 5-10 .0.,aboveathemeltingrpointiof the polymer. This isforEthezpurposenfiavoiding excessive exposure of the. polymer-:tozelevated temperatures,v :i. e.,; above 'thezmelting: point.
While antimony trifiuoride is the vprefen ed catalyst, any antimony-.compnun'dxfrom the:group, consisting of antimony .trioxi'dez and antimony trihalides, such .as antimony :tri'chl'oritle, anti mony .tribromiderand antimony tri-ti'oiiili'e :e'fieetively catalyzes the reaction. Catalyst-concentrations ranging .from 0:01???) ttoil';li%- ='mayr be employed, andv 0.03%, iba'sedfsupon the weight of glycolide or combined weiglitstof glycolide land lactide 101 other lacti'cles, ii's preferred. Usually; when the'catalyst concentration-is decreasedibelow- 0.01% or increased -:a;bove.;0sls%', them'elt: viscosity of the 'resulting- -polym-eriis l'ower than that which may be obtained-ioperating withinithe specified range of catalyst concentration.
The process of the present invention zmay be employed with advantage toprepare copolymers of glycolide withsmall quantities-e. g-., up' 'to 15%, of other lactidos such as "lactide and 'disalicylide. For example,- the preparation of acopolymerof /10 -glycolideilactide"offers two advantagesoverthe 'homopolymer-'of "g'lycolide; One advantage is thatthe melting"point-ofthe copolymer is lower than "the homopolymerf-b eing in the neighborhood of 200 6. and the entire reaction can be conducted alt-approximately -the melting point ofthecopolymer; Operation-'afith e lower temperaturesdecreases thera'teoi? degradation of the polymer which "gives aipoiymer'oi, lighter color. Another advantage thatjthe copolymer can:.be successiully 'quenched vhenibeing extruded into film because ithecopolymer fis; less cryst lline. 1 Oni'the "other. hand; hefhomap yme ho 'ajs ater tendency torrystalli e.
on "extrusionrandthfereby tendsjtojform'fopaque.
areas in the film.
The presence of water or acid impurities in glycolide tends to retard polymerization, and the resulting polyhydroxyacetic ester will not have a molecular weight suitable for extrusion into films or filaments. For example, polymerization of impure glycolide usually results in the formation of a polymer having a melt viscosity less than 400 poises, while pure glycolide gives polymers having melt viscosities up to 50,000 poises. However, polyhydroxyacetic esters having melt viscosities substantially greater than 27,000 poises are extremely difiicult to extrude into films or filaments.
Pure, dry (i. e., anhydrous) glycolide may conveniently be prepared in high yield by the depolymerization of low molecular weight polyhydroxyacetic ester which is formed as a by-product in various known processes of converting hydroxyacetic acid directly to high molecular weight polyhydroxyacetic ester. The following example typifies the preparation of glycolide by this method:
Example A A charge of 4,000 parts of crude hydroxyacetic acid flake was heated at atmospheric pressure until the temperature of the liquid reached 175- 185 C. The temperature was maintained at this range for 2 hours or silghtly longer until water ceased to distill. The pressure was then reduced over a period of /2 hour to 150 mm. of mercury; and the temperature was maintained between 175-185 C. for 2 hours, or, again for a slightly longer time, until water ceased to distill. The product obtained was poured into an enamel pan and, after solidification, the white, brittle polymer was reduced to a free-flowing powder in a cutting machine. 2,972 parts of polyhydroxyacetic ester (low molecular weight material having a melt viscosity of less than 50 poises) were obtained (97.4% of the theoretical amount) while the water collected amounted to 932 parts (98.2% of the theoretical amount). The 9'7 parts unaccounted for (2.4%) were lost on transfer.
The apparatus for depolymerizing the above polyhydroxyacetic ester to form glycolide consisted of a three-necked reaction vessel equipped with a stainless steel stirrer, and provision for introducing the powdered polymer in increments through one neck and for take-on of the glycolide distillate through a downward connection tube wound with an electrical strip heater. A supply vessel containing the powdered polymer was attached by means of heavy-walled, flexible tubing to a stopcock so that the portion above the stopcock could be alternately filled and discharged into the reaction vessel. A steady stream of nitrogen was introduced through the polymer inlet tube to prevent accumulation or" glycolide distillate and consequent plugging. A receiver was cooled in an ice water bath and equipped with an air condenser to trap most of the uncondensed glycolide. Since the nitrogen stream tended to carry glycolide beyond the receiver, three traps Were interposed to protect the pump. One trap was a three-necked vessel filled with steel wool and immersed in an ice water bath, and the other two were standard Dry Ice-acetone tra s.
1 000 parts of powdered, low molecular weight polymer produced as previously described were thoroughly mixed with 10 parts of antimony trioxide and placed in the supply vessel. The polymer was introduced from the supp y vessel into the reaction vessel maintained at 270-285 C. at
4 the rate of 200 parts per hour in five-part increments with the pressure of the system maintained at 12-15 mm. of mercury. A 93% yield of crude glycolide distillate was collected as a white to light yellow solid in the receiver.
Polymerization of the crude glycolide as obtained according to the above process showed that it was necessary to purify the crude glycolide in order to obtain high yields of high molecular weight polyhydroxyacetic ester. The glycolide was purified by 2 or 3 recrystallizations from chemically pure ethyl acetate. In all cases, the crude glycolide was added to approximately twice its weight of ethyl acetate; solution was efiected at the boiling point; decolorizing charcoal was added; and reflux continued for hour. The solution was filtered while hot; cooled; and white glycolide crystals were obtained on filtering and drying. Further recrystallizations were conducted in a similar manner, but the decolorizing charcoal treatment was omitted.
The following examples of preferred embodiments will further serve to illustrate the principles and practice of the process of the present invention. Parts and percentages are by weight unless otherwise indicated:
In each of the following examples, pure glycolide, free from traces of water and acid impurities and having a melting point between 83.8-84.3" 0., was employed.
Example 1 Antimony trifiuoride (0.03% by weight of dry glycolide) was added to 2,300 parts of pure, dry glycolide in a closed reaction vessel. Nitrogen was allowed to pass over the surface of the material in the vessel. The reaction vessel was heated to C. by means of an oil bath and the contents stirred for one hour at that temperature. Stirring was stopped at this point since the material had become too viscous; and heating at 195 C. was maintained for one more hour, after which the temperature was quickly raised to 230 C. and maintained for hour. After solidification, the resulting polymer (M. P. 215-220 C.) was pulverized and further dried. The resulting polyhydroxyacetic ester had a melt viscosity of 20,000 poises at 245 C. and 6,900 poises at 255 C. The ground polymer was extruded into a tough, colddrawable, stretchable, and self-supporting film. The film had a melt viscosity of 1,800 poises at 245 C.
The most characteristic single indication of plastic properties in high molecular weight polyhydroxyacetic esters is the ability of the polymer to form a highly viscous melt. Since the polymers degrade with increasing rapidity as the temperature is raised above the melting point, a standard temperature of 245 C. was selected for comparative tests. This is near the melting point but is sufficiently above it to avoid melting difiiculties. It has been found that at 245 C. a polyhydroxyacetic ester must have a melt viscosity, measured by the method of Flory (Journal of the American Chemical Society, 62, 1057 (1940) of at least 400 poises before it can be molded into useful shaped articles, the preferred viscosity range being from 1,000 to 10,000 poises for extrusion into fibers and films. Below this limit, the polymer melt is too fluid and non-adherent to handle properly during forming operations; and the shaped products are increasingly brittle, non-cohesive and weak. On the other hand, the melt viscosity can be so high that the polymer is difficult to mold or extrude.
Example 2 Antimony trichloride (approximately 0.10% by 1 Example 3 Antimony trioxide (0.03% by weight of dry glycolide) was added to 20.0 parts of pure, dry glycolide in a tubular reaction vessel (diameter 0.5") provided with a side-arm near the top of the tube. Nitrogen was allowed to pass over the surface of the material in the tube end out through the side-arm. The tube was heated to 155 C. by means of a vapor bath and maintained at that temperature for 2 hours. Then the temperature was raised to 241 C. in an appropriate vapor bath. After 1.8 hours at 241 C., a polymer was produced having a melt viscosity of 4,300 poises at 241 0.
Example 4 Antimony trifiuoride (0.03% based upon the combined weight of glycolide and lactide) was added to 4.5 parts of pure, dry glycolide and 0.5 part of pure, dry lactide in a reaction vessel. Nitrogen was allowed to pass over the surface of the material in the vessel. The reaction vessel was heated to 195-200 C. by means of an oil bath and maintained at that temperature for 2% hours. Stirring of the reaction mixture was stopped after one hour because the material became too viscous. The resulting polymer was allowed to cool, and the solidified material was pulverized to a powder. After further drying, the
polymer (M. P. ZOO-205 C.) had a meltviscosity of 15,000 poises at 218 C. and a melt viscosity of 7,000 poises at 245 C. The polymer was extruded into a tough, clear, cold-drawable, stretchable and self-supporting film at 210 C. The resulting film had a melt viscosity of 1,300 poises at 218 C.
A particular advantage of the present invention is that it provides a process of forming high molecular weight polyhydroxyacetic esters by polymerizing a by-product of known processes for preparing the polymeric ester, glycolide. A
made without departing from the'spirit and scope of my invention, it is to be understood that said invention is in no way restricted save as set forth in the following claims.
I claim:
1. A process for preparing polyhydroxyacetic esters which comprises polymerizing glycolide by heating glycolide, free of Water and acid impurities, at a temperature of from about C. to about 245 C. in the presence of a catalytic amount of an antimony compound from the group consisting of antimony trioxide and antimony trihalides.
2. A process for preparing polyhydroxyacetic esters which comprises heating glycolide, free of water and acid impurities, at a temperature of from about 150 C. to about 245 C. in the presence of from 0.01% to 1.0% by weight, based on the weight of glycolide, of an antimony compound from the group consisting of antimony trioxide and antimony trihalides.
3. The process of claim 2 wherein the polymerization is carried out in an inert atmosphere.
4. The process of claim 2 wherein 0.03% by weight of antimony compound is used.
5. The process of claim 2 wherein the antimony compound is antimony trifiuoride.
6. A process for preparing polyhydroxyacetic ester homopolymer which comprises polymerizing lycolide by initially heating glycolide, free of water and acid impurities, in an atmosphere of inert gas, at a temperature of from 150 C. to 200 0., to form a low molecular weight polymer, and thereafter heating the polymer at a temperature of from 220 C. to 245 C. until a polymer having a melt viscosity at 245 C. of at least 400 poises is obtained, the entire reaction being carried outin the presence of from 0.01% to 1.0% by weight, based on the weight of glycolide, of an antimony compound from the group consisting of antimony trioxide and antimony trihalides as catalyst.
7. The process of claim 6 wherein the polymerization reaction is carried out in an atmosphere of nitrogen gas and in the presence of about 0.03% by weight, based on the weight of glycolide, or antimony trifluoride.
CHARLES E. LOWE.
References Cited in the file of this patent UNITED STATES PATENTS Number

Claims (1)

1. A PROCESS FOR PREPARING POLYHYDROXYACETIC ESTERS WHICH COMPRISES POLYMERIZING GLYCOLIDE BY HEATING GLYCOLIDE, FREE OF WATER AND ACID IMPURITIES, AT A TEMPERATURE OF FROM ABOUT 150* C. TO ABOUT 245* C. IN THE PRESENCE OF A CATALYTIC AMOUNT OF AN ANTIMONY COMPOUND FROM THE GROUP CONSISTING OF ANTIMONY TRIOXIDE AND ANTIMONY TRIHALIDES.
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Cited By (114)

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US3440225A (en) * 1963-03-23 1969-04-22 Wolfen Filmfab Veb Process for the manufacture of shaped structures from polyglycolides
US3442871A (en) * 1966-05-04 1969-05-06 American Cyanamid Co Process for polymerizing a glycolide
US3457280A (en) * 1967-06-12 1969-07-22 American Cyanamid Co Alpha-glycolide and methods for the isolation thereof
US3468853A (en) * 1966-06-15 1969-09-23 American Cyanamid Co Process of polymerizing a glycolide
US3636956A (en) * 1970-05-13 1972-01-25 Ethicon Inc Polylactide sutures
US3797499A (en) * 1970-05-13 1974-03-19 Ethicon Inc Polylactide fabric graphs for surgical implantation
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US3982543A (en) * 1973-04-24 1976-09-28 American Cyanamid Company Reducing capillarity of polyglycolic acid sutures
US4048256A (en) * 1976-06-01 1977-09-13 American Cyanamid Company Normally-solid, bioabsorbable, hydrolyzable, polymeric reaction product
US4095600A (en) * 1976-06-01 1978-06-20 American Cyanamid Company Normally-solid, bioabsorbable, hydrolyzable, polymeric reaction product
US4243775A (en) * 1978-11-13 1981-01-06 American Cyanamid Company Synthetic polyester surgical articles
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